U.S. patent number 5,376,522 [Application Number 08/111,263] was granted by the patent office on 1994-12-27 for silver halide photographic material.
This patent grant is currently assigned to Konica Corporation. Invention is credited to Nobuaki Kagawa, Tomoyuki Nakayama, Hakubun Ohashi, Hideki Takiguchi.
United States Patent |
5,376,522 |
Takiguchi , et al. |
December 27, 1994 |
Silver halide photographic material
Abstract
A silver halide photographic material having photographic
constituent layers on a support, which photographic material is
characterized in that at least one of said photographic constituent
layers is a silver halide emulsion layer, at least 50% in number of
the light-sensitive silver halide grains in said silver halide
emulsion layer being grains that contain at least 60 mol % of
silver bromide, and at least one of said photographic constituent
layers containing at least one of the compounds represented by the
following general formula (I): where L is a 1igand in a 5- or
6-membered hetero ring; X is an anionic group; l is an integer of
0-2; m is an integer of 1 or 2; n is an integer of 1-3; p is an
integer of 0-3; and q is an integer of 1-4. The silver halide
photographic material has high sensitivity and yet it is improved
in protection against deterioration in its photographic performance
such as increased fog and degraded granularity due to storage after
manufacture.
Inventors: |
Takiguchi; Hideki (Hino,
JP), Nakayama; Tomoyuki (Hino, JP), Kagawa;
Nobuaki (Hino, JP), Ohashi; Hakubun (Hino,
JP) |
Assignee: |
Konica Corporation (Tokyo,
JP)
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Family
ID: |
26407435 |
Appl.
No.: |
08/111,263 |
Filed: |
August 24, 1993 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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667192 |
Mar 8, 1991 |
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Foreign Application Priority Data
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Mar 16, 1990 [JP] |
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2-66257 |
Jul 5, 1990 [JP] |
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2-178834 |
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Current U.S.
Class: |
430/567; 430/600;
430/605; 430/612; 430/614 |
Current CPC
Class: |
G03C
1/09 (20130101); G03C 1/34 (20130101) |
Current International
Class: |
G03C
1/09 (20060101); G03C 1/34 (20060101); G03C
001/035 (); G03C 001/09 () |
Field of
Search: |
;430/567,600,605,612,614 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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313949 |
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May 1989 |
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EP |
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264525 |
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Feb 1989 |
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DD |
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Other References
Trivelli et al., Phot. J., 79,330 (1939). .
Journal fur Signalaufzeichnungmaterialien, 5, No. 6, pp. 449-455,
Nov. 1977..
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Primary Examiner: Baxter; Janet C.
Attorney, Agent or Firm: Frishauf, Holtz, Goodman &
Woodward
Parent Case Text
This application is a continuation of application Ser. No.
07/667,192, filed Mar. 8, 1991 (abandoned).
Claims
What is claimed is:
1. A silver halide photographic material having photographic
constituent layers on a support, wherein at least one of said
photographic constituent layers is a silver halide emulsion layer,
at least 50% in number of the light-sensitive silver halide grains
in said silver halide emulsion layer being grains that contain at
least 60 mol % of silver bromide, said grains having a core/shell
structure, said core having a higher iodide content than said
shell, and at least one of said silver halide emulsion layers
containing at least one of the compounds represented by the
following general formula (I):
[H.sub.l Au.sub.m (L).sub.n (X).sub.p ].sub.q (I)
where L is a ligand in a 5- or 6-membered hetero ring; X is an
anionic group; l is an integer of 0-2; m is an integer of 1 or 2; n
is an integer of 1-3; p is an integer of 0-3; and q is an integer
of 1-4.
2. The silver halide photographic material according to claim 1
wherein the compound of formula (I) is selected from the group
consisting of ##STR5##
3. The silver halide photographic material according to claim 1
wherein the compound represented by the general formula (I) is
contained in an amount of 1.times.10.sup.-4 to 1.times.10.sup.-8
mole per mole of silver halide.
4. The silver halide photographic material according to claim 3
wherein the compound represented by the general formula (I) is
contained in an amount of 1.times.10.sup.-5 to 1.times.10.sup.-8
mole per mole of silver halide.
Description
BACKGROUND OF THE INVENTION
This invention relates to silver halide photographic materials,
more particularly to a technique for reducing the increase in
fogging and the resultant deterioration in granularity during
prolonged storage of high-sensitivity photographic materials.
The recent advances in various sensitizing techniques have been
remarkable and ultrahigh-sensitivity color photographic materials
having speeds of 1000 and above in ISO designation are commercially
available today. Heat- or moisture-initiated fogging during
prolonged storage has been a well known problem with
high-sensitivity photographic materials but the advent of more
sensitive products has highlighted new problems that should by no
means be neglected and they are the increase in fogging due to the
effects of so-called "natural radiations" (i.e., environmental
radiation and cosmic rays) and the resulting deterioration in
granularity.
It has been reported that the fogging due to prolonged storage of
high-sensitivity silver halide photographic materials and the
resultant deterioration in granularity depend upon the inherent
sensitivity of silver halide grains, the contents of silver and
gold in photographic materials and the amount of potassium ions.
Under these circumstances, the present inventors noted gold
sensitizers as one of the factors to aging deterioration during
prolonged storage of high-sensitivity photographic materials.
Inorganic gold complex salts have been commonly used as gold
sensitizers (see, for example, U.S. Pat. No. 2,399,083). Among the
inorganic gold complex salts, chloroauric acid, potassium
chloroaurate, potassium aurithiocynate and auric trichloride are
currently used as advantageous gold sensitizers. However, these
gold complex salts are prone to liberate gold and part of the
liberated gold will form a stronger complex with gelatin and remain
in the latter thereafter. Hence, deterioration in the performance
of photographic materials that results from the use of gold
sensitizers can be dealt with as a problem associated with the
chemical properties of the gold sensitizers.
SUMMARY OF THE INVENTION
An object, therefore, of the present invention is to provide a
high-sensitivity silver halide photographic material that is
improved in protection against deterioration in its photographic
performance such as increased fog and degraded granularity due to
storage after manufacture.
As a result of the intensive studies conducted in order to attain
this object, the present inventors found that it could be achieved
by the following and the present invention has been accomplished on
the basis of this finding.
(1) A silver halide photographic material having photographic
constituent layers on a support, at least one of said photographic
constituent layers being a silver halide emulsion layer, at least
50% in number of the light-sensitive silver halide grains In the
silver halide emulsion layer being grains that contain at least 60
mol % of silver bromide, and at least one of said photographic
constituent layers containing at least one of the compounds
represented by the following general Formula (I):
(where L is a ligand in a 5- or 6-membered hetero ring; X is an
anionic group; l is an integer of 0-2; m is an integer of 1 or 2; n
is an integer of 1-3; p is an integer of 0-3; and q is an integer
of 1-4); and
(2) A process for producing a silver halide photographic material
that contains in at least one photographic constituent layer silver
halide grains at least 50% in number of which are grains that
contain at least 60 mol % of silver bromide, which process is
characterized in that silver halide grains are chemically ripened
in the presence of a compound represented by the general formula
(I).
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (I), X represents an anionic group as
exemplified by a halide ion (e.g. fluoride, chloride, bromide or
iodide ion), a perchlorate ion, a borofluorate ion, a sulfate ion,
a nitrate ion and a thiocyanate ion. The ligand in a 5- or
6-membered hereto ring that is represented by L may be an anionic,
cationic or neutral monocyclic group which is selected from among
the groups represented by the following general formulas (II) and
(III): ##STR1##
In the general formulas (II) and (III), Y.sub.1 and Y.sub.2 each
represents an oxygen atom, a sulfur atom, a selenium atom or
.dbd.NR.sub.1 group; Z.sub.1 -Z.sub.5 each represents ##STR2##
.dbd.C(R.sub.3)--, .C.dbd.W, .dbd.NR.sub.1, --N.dbd., an oxygen
atom, a sulfur atom or a selenium atom; at least one of Z.sub.1
-Z.sub.4 represents .dbd.C.dbd.W or .dbd.CHSH, provided that W
represents an oxygen atom, a sulfur atom, a selenium atom or
NR.sub.1, that R.sub.1 represents a hydrogen atom, an alkyl group,
an aryl group or a heterocyclic group, and that R.sub.2 and R.sub.3
each represents an alkyl group, an aryl group, a heterocyclic
group, a halogen atom, a hydroxyl group, a mercapto group, an
alkoxy group, an alkylthio group, an aryloxy group, an arylthio
group, a heteroxy group, a heterothio group, an amino group, a
phosphonyl group, a carboxyl group, an alkoxycarbonyl group, an
aryloxycarbonyl group, a sulfo group, an imido group, a carbamoyl
group, a sulfamoyl group, an acyl group, a cyano group, an acyloxy
group, a carbamoyloxy group, a silyloxy group, a ureido group, a
sulfamoylamino group, a nitro group, a sulfonyl group, a sulfinyl
group, an acylamino group, an alkoxycarbonylamino group, an
aryloxycarbonyloxy group, a sulfonamido group.
In the general formula (II), Y.sub.1 and Z.sub.1 -Z.sub.4 combine
together to form a 5-membered hetero cyclic group as exemplified by
the following groups: pyrrole groups such as 2(1H)-pyrroline,
2-pyrrolidinium, 2(3H)-pyrroline and pyrronium groups; imidazole
groups such as 2(3H)-imidazoline, 2-imidazolinium,
2(3H)-imidazoline and imidazolium groups; oxazole groups such as
2(3H)-oxazolidine, 2-oxazolinium, 2(3H)-oxazoline and oxazolium
groups; isoxazole groups such as 3(2H)-isoxazoline and
3-isoxazolium groups; thiazole groups such as 2(3H)-thiazolium,
2-thiazolium, 2(3H)-thiazoline and thiazolium; isothiazole groups
such as 3(2H)-isothiazoline and 3-isothlazolium groups; selenazole
groups such as 2(3H)-selenazolidine and selenazolium; oxazolldlne
groups such as 2-thio-oxazolidine-2,4-dione, 2,4-oxazolidinedione,
oxazolidin-4-one and 2-oxazolin-4-one groups; thiazolidine groups
such as 2-thio-thiazoline-2,4-dione, 2,4-thiazolidinedione,
thiazolidin-4-one and 2-thiazolin-4-one groups; imidazolidine
groups such as 2-thio-imidazolidine-2,4-dione,
2,4-imidazolidinedione, isothiazolidin-4-one and
2-imidazolidin-4-one groups; and selenazolidine groups such as
2-thio-selenazolidine -2,4-dione, 2,4-selenazolidinedione,
selenazolidin-4-one and 2-selenazolin-4-one groups.
In the general formula (III), Y.sub.2 and Z.sub.1 -Z.sub.5 combine
together to form a 6-membered heterocyclic group as exemplified by
the following groups: pyridine groups such as
1,2-dihydro-2-pyridylidene, 2-pyridinium,
tetrahydropyridine-2,4-dione and tetrahydropyridine-2,6-dione
groups, pyrimidine groups such as tetrahydropyrimidine-2,4-dione,
tetrahydropyrimidine-2,6-dione, hexahydropyridine-2,4,6-trione and
2-thiohexahydropyridine-2,4,6-trione groups; and pyrazoline groups
such as pyrazolin-5-one and pyrazolidine-3,5-dione groups.
Examples of R.sub.1 -R.sub.3 in the substituents on the hetero
rings in the general formulas (II) and (III) are given below: alkyl
groups such as straight or branched unsubstituted alkyl groups
(e.g. methyl, ethyl, propyl, amyl, 2-ethylhexyl, dodecyl,
2-hexyldecyl and octadecyl), cycloalkyl groups (e.g. cyclopentyl
and cyclohexyl) and substituted alkyl groups (e.g. 2-carboxyethyl,
2-hydroxyethyl, 2-methanesulfonylaminoethyl, 2-methoxyethy,
2-(2-methoxyethoxy)ethyl, 2-methanesulfonylethyl, 3-sulfopropyl and
trifluoromethyl); aryl groups including both substituted and
unsubstituted aryl groups such as phenyl, 4-t-butylphenyl,
2,4-di-t-amylphenyl, 4-nitrophenyl, 3-nitrophenyl,
4-methanesulfonylphenyl, 3-methanesulfonylaminophenyl,
2,4,6-trichlorophenyl, 4-trifluorophenyl, 2-methoxyphenyl,
2-acetylaminophenyl and 2-(2-ethylureido)phenyl; and heterocyclic
groups, which may be substituted or unsubstituted, including
2-pyridine, 2-furyl, 2-pyrimidyl, 2-thienyl, 5-nitro-2-thienyl,
4-methyl-2-thiazolyl and 1-pyrodinyl.
Other examples of R.sub.2 and R.sub.3 are listed below: halogen
atoms such as fluorine, chlorine, bromine and iodine atoms; alkoxy
groups, which may be substituted or unsubstituted, including
methoxy, ethoxy, propoxy, 2-methoxyethoxy, 2-methylthioethoxy,
2-methanesulfonylethoxy and 2-dodecyloxy groups; aryloxy groups,
which may be substituted or unsubstituted, including phenoxy,
2-methylphenoxy and 4-t-butylphenoxy groups; heteroxy groups such
as 1-phenyltetrazol-5-oxy and 2-tetrahydropyranyloxy groups;
acyloxy groups such as acetoxy and butanoyloxy groups; carbamoyloxy
groups such as methylcarbamoyloxy and phenylcarbamoyloxy groups;
silyloxy groups such as trimethylsiloxy and dibutylmethylsilyloxy
groups; alkylthio groups, which may be substituted or
unsubstituted, including methylthio, octylthio, tetradecylthio,
octadecylthio, 3-phenoxypropylthio and
3-(4-t-butylphenoxy)propylthio groups; arylthio groups such as
phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio and 4-tetradecanamidophenylthio groups;
heterothio groups such as 2-benzothiazolylthio,
2,4-diphenoxy-1,3,5-triazole-6-thio and 2-pyridylthio groups;
acylamino groups such as acetamido, butanamido and benzamido
groups; amino groups such as amino, anilino, 2-hydroxyanilino,
2-mercaptoanilino, N-acetylanilino, methylamino and
N,N-diethylamino groups; ureido groups such as 2-phenylureido,
2-methylureido and 2,2-dibutylureido groups; sulfamoylamino groups
such as N,N-dipropylsulfamoylamino and
N-methyl-N-decylsulfamoylamino groups; sulfonamido groups such as
methanesulfonamido, butanesulfonamido, hexanesulfonamido,
benzenesulfonamido, p-toluenesulfonamido and
2-methylthio-5-hydroxybenzenesulfonamido groups;
alkoxycarbonylamino groups such as methoxycarbonylamino and
butoxycarbonylamino groups; aryloxycarbonylamino groups such as a
phenoxycarbonylamino group; carbamoyl groups such as
N-ethylcarbamoyl, N,N-dibutylcarbamoyl,
N-(2-methoxydlethyl)carbamoyl and N,N-dimethylcarbamoyl groups;
sulfamoyl groups such as N-ethylsulfamoyl, N,N-dipropylsulfamoyl
and N,N-dimethylsulfamoyl groups; sulfonyl groups such as
methanesulfonyl, butanesulfonyl, benzenesulfonyl and
p-toluenesulfonyl groups; sulfinyl groups such as ethanesulfinyl
and 3-phenoxypropylsulfinyl groups; phosphonyl groups such as
phenoxyphosphonyl, ethoxyphosphonyl and phenylphosophonyl groups;
alkoxycarbonyl groups such as methoxy carbonyl and butoxycarbonyl
groups; aryloxycarbonyl groups such as phenoxycarbonyl and
p-anisldyl groups; acyl groups such as acetyl, 3-carboxypropanoyl,
benzoyl and p-mercaptobenzoyl groups; and imido groups such as
N-succinylimido, N-phthalimido and 3-allylsuccinylimido groups.
The following are specific but non-limiting examples of the
compounds of the general formula (I) that can be used in the
present invention. ##STR3##
The gold compounds to be used in the present invention can be
synthesized by known methods such as those described in Bull. Chem.
Soc. Japan, 48 (3), 1024-1029, 1975, J. Inorg. Nucl. Chem., Vol. 38
(1), 7-11, 1976, Transition Met. Chem., Vol. 2 (6), 224-227, 1977,
and Unexamined published Japanese Patent Application No.
147537/1989.
The gold compounds thus synthesized are preferably added to silver
halide emulsions as solutions in water or water-miscible solvents
such as methanol, ethanol, and fluorinated alcohols, which may be
used either alone or as admixtures. Gold compounds that are
slightly soluble in appropriate solvents are preferably added in
the form of dispersions.
The gold compounds may be added at any stage of the process of
emulsion preparation but they are preferably added at the start of,
during or just before the completion of chemical ripening.
The amount in which the gold compounds are to be used varies with
such factors as the type of silver halide emulsion, the type of
gold compound used and the conditions of ripening. Preferably, they
are used in amounts of 1.times.10.sup.-4 to 1.times.10.sup.-8 mole
per mole of silver halide, with the range of 1.times.10.sup.-5 to
1.times.10.sup.-8 mole being more preferred.
In the present invention, chemical ripening may be performed in
combination with the use of other chemical sensitizers such as
sulfur sensitizers. A suitable sulfur sensitizer may be selected
from among sulfur crystals, water-soluble sulfide salts,
thiosulfates, thioureas. mercapto compounds and rhodanines.
Specific examples of these compounds are described in U.S. Pat.
Nos. 1,574,944, 2,410,689, 2,278,947, 3,501,313, 3,656,955, West
German Patent No. 1,422,869, and Japanese Patent Publication Nos.
20533/1974 and 28568/1983. Among these compounds, thiosulfates,
thioureas and rhodanines are particularly preferred.
Other chemical sensitizers that can be used in chemical ripening
include: selenium compounds of the types described in U.S. Pat.
Nos. 3,420,670, 3,297,447 and Unexamined Published Japanese Patent
Application No. 71320/1975; reducing materials such as amines and
stannous salts of the types described in U.S. Pat. Nos. 2,487,850,
2,518,698, 2,521,925, 2,521,926, 2,419,973, 2,694,637 and
2,983,610; and salts of noble metals such as platinum, palladium,
iridium and rhodium of the types described in U.S. Pat. Nos.
2,448,060, 2,566,245 and 2,566,263.
In the present invention, good results are often obtained if
chemical ripening with the gold compounds is performed in the
presence of silver halide solvents such as thiocyanates, thioethers
and 4-substituted thiourea.
Chemical ripening with the gold compounds can also be performed in
the presence of chemical sensitization aids (chemical sensitization
modifiers). Useful chemical sensitization aids (modifiers) are
compounds such as 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene,
guanosinc and sodium p-toluenesulfinate. Specific examples of
chemical sensitization aids (modifiers) are described in U.S. Pat.
Nos. 2,131,038, 3,411,914, 3,554,757, Unexamined Published Japanese
Patent Application No. 126526/1983, and G. F. Duffin, "Photographic
Emulsion Chemistry", The Focal Press, pp. 138-143, 1966.
The emulsion being subjected to chemical ripening preferably has a
pAg (the logarithm of the reciprocal of silver ion concentration)
of 7.0-11.0. The pit of the emulsion is preferably in the range of
4.0-9.0. The temperature for chemical ripening is preferably in the
range of 40.degree.-90.degree. C.
The gold compounds of the general formula (I) can also be used
preferably to insure that silver sulfide clusters grown and formed
selectively at specific sites on the surfaces of silver halide
grains by slowly adding sulfur sensitizers over time are converted
to effective gold-silver sulfide clusters. For the techniques of
selectively growing silver sulfide clusters, see Unexamined
Published Japanese Patent Application No. 93447/1986.
The silver halide emulsion to be used in the present invention is
preferably composed of silver bromide, silver iodobromide, silver
iodochlorobromide of silver chlorobromide. At least 50% in number
of the silver halide grains must contain 60 mol % or more of silver
bromide. Desired silver halide emulsions can be prepared by known
methods such as those described in P. Glafkides, "Chimie et
Physique Rhotographique", Paul Montel, 1967, G. F. Duffin,
"Photographic Emulsion Chemistry", The Focal Press, 1966, V. L.
Zelikman et al., "Making and Coating Photographic Emulsions", The
Focal Press, 1964.
Reverse precipitation, or the formation of grains In the presence
of excess silver ions, can also be employed. As one version of
double-jet precipitation, a "controlled double-jet method" can also
be performed with a constant pAg being maintained in the liquid
phase where silver halide is formed.
The silver halide emulsion to be used in the present invention may
have a narrow or broad size distribution of silver halide
grains.
The silver halide grains incorporated in the silver halide emulsion
to be used in the present invention may have various
crystallographic shapes such as regular forms (e.g. cubes,
octahedra and tetradecahedra), anomalous forms (e.g. spheres),
twinned faces, or combinations of these forms, The structure of
silver halide crystals may be such that they have a substantially
uniform composition, or they have a dual (core/shell) structure or
a multi-layered structure, with a core/shell structure being
preferred. In the case of silver halide grains having a core/shell
structure, the interior (core) and the surface layer (shell)
preferably have dissimilar halide compositions.
The gold compounds of the general formula (I) can also be used in
sensitizing emulsions composed of tabular silver halide grains.
Tabular silver halide grains are those which have a diameter to
thickness ratio of at least 3. The "diameter" of a tabular silver
halide grain means the diameter of a circle whose area is equal to
the projected area of that grain, and the "thickness" is defined by
the distance between two parallel faces by which the tabular grain
is bounded. For the composition and structure of tabular silver
halide grains, see the above description of silver halide
grains.
The silver halide crystal grains in the silver halide emulsion to
be used in the present invention may have silver halides of
different compositions epitaxy-joined to matrix silver halide
crystals. Alternatively, the matrix may be joined to other
compounds than silver halides such as silver thiocyanate and lead
oxide. The formation of silver halide grains or their physical
ripening may be performed in the presence of compounds of
chalcogens such as sulfur, selenium and tellurium, or cadmium
salts, zinc salts, lead salts, thallium salts, iridium salts or
complex salts thereof, or rhodium salts or complex salts thereof,
or iron salts or complex salts thereof.
The interior of silver halide crystals may be subjected to
reduction sensitization as described in Japanese Patent Publication
No. 1410/1983 and Moisar et al., "Journal of Photographic Science",
25, 19-27, 1977.
Two or more separately prepared silver halide emulsions may be used
as admixtures of suitable proportions in the present invention.
The silver halide emulsion to be used in the present invention may
be spectrally sensitized with methine dyes and any other known
dyes. Useful spectral sensitizers are described in, for example,
German Patent No. 929,080, U.S. Pat. Nos. 2,231,658, 2,493,748,
2,503,776, 2,519,001, 2,912,329, 3,655,394, 3,656,959, 3,672,897,
3,694,217, BP No. 1,242,588, and Japanese Patent Publication No.
14030/1969. These spectral sensitizers may be used either on their
own or as admixtures. Combinations of spectral sensitizers are
often used for the particular purpose of super-sensitization, with
typical examples of combined spectral sensitizers being described
in U.S. Pat. Nos. 268,545, 2,977,229, 3,397,060, 3,522,052,
3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,679,428, 3,703,377,
3,769,301, 3,814,609, 3,837,862, BP No. 1,344,281, Japanese Patent
Publication No. 4936/1968, etc.
In addition to spectral sensitizers, the emulsion may contain dyes
that have no spectrally sensitizing capability by themselves or
those materials which are substantially incapable of absorbing
visible light but which exhibit a supersensitizing effect. For
example, the emulsion may contain aminostilbene compounds
substituted by nitrogenous heterocyclic groups (as described in
U.S. Pat. Nos. 2,933,390 and 3,635,721), condensates of aromatic
organic acids and formaldehyde (as described in U.S. Pat. No.
3,743,510), cadmium salts or azaindene compounds. The combinations
described in U.S. Pat. Nos. 3,615,613, 3,615,641, 3,617,295 and
3,635,721 are particularly useful.
For spectral sensitization of the silver halide emulsion used in
the present invention, spectral sensitizers may be added at any
stage, such as prior to, during or after the completion of chemical
sensitization but good results are often obtained if the
sensitizers are added before the start of chemical
sensitization.
For the purpose of increasing sensitivity, contrast or the speed of
development, the silver halide emulsion to be used in the present
invention may contain various additives including polyalkylene
oxides or derivatives thereof such as ethers, esters or amines,
thioether compounds, thiomorpholines, quaternary ammonium
compounds, urethane derivatives, urea derivatives, imidazole
derivatives and 3-pyrazolidones. Useful compounds are described in
U.S. Pat. Nos. 2,400,532, 2,423,549, 2,716,062, 3,617,280,
3,772,021 and 3,808,003.
The silver halide emulsion to be used in the present invention may
also contain antifoggants and stabilizers. Useful compounds are
described in Product Licensing Index, Vol. 92, p. 107 under
"Antifoggants and stabilizers".
Known photographic addenda may be used in the silver halide
emulsion. Compounds that are within the class of known photographic
addenda are described in Research Disclosure (RD), No. 17643
(December 1978) and No. 18716 (November 1979) and summarized in the
following table.
______________________________________ Addenda RD-17643 RD-18716
______________________________________ Chemical sensitizer p. 23
III p. 648, upper right column Spectral sensitizer p. 23 IV p. 648,
upper right column Development p. 29 XXI p. 648, upper right
accelerator column Antifoggant p. 24 VI p. 649, lower right column
Stabilizer p. 24 VI p. 649, lower right column Anti-color stain
agent p. 25 VII p. 650, left and right columns Image stabilizer p.
25 VII UV absorber pp. 25-26 VII p. 649, right column to p. 650,
left column Filter dye pp. 25-26 VII p. 649, right column to p.
650, left column Optical brightening p. 24 V agent Hardener p. 26 X
p. 651, right column Coating aid pp. 26-27 XI p. 650, right column
Surfactant pp. 26-27 XI p. 650, right column Plasticizer p. 27 XII
p. 650, right column Slip agent p. 27 XII Antistatic agent p. 27
XII p. 650, right column Matting agent p. 28 XVI p. 650, right
column Binder p. 26 IX p. 651, right column
______________________________________
Emulsion layers in the silver halide photographic material of the
present invention may incorporate dye-forming couplers that form
dyes upon couling reaction with the oxidation product of aromatic
primary amino compounds as developing agents (e.g.
p-phenylenediamine derivatives and aminophenol derivatives) during
color development. Dye-forming couplers are commonly selected in
such a way that they form dyes that absorb spectral light to which
the associated emulsion layers are sensitive. Thus, yellow dye
forming couplers are used with a blue-sensitive emulsion layer,
magenta dye forming couplers with a green-sensitive emulsion layer,
and cyan dye forming couplers with a red-sensitive emulsion layer.
However, various silver halide color photographic materials may be
prepared using other combinations depending on a specific
object.
The dye-forming couplers desirably have ballast groups in their
molecule that have at least 8 carbon atoms and that render the
couplers non-diffusible. The dye-forming couplers may be
four-equivalent couplers that require four molecules of silver ion
to be reduced to form one molecule of dye, or two-equivalent
couplers that need only two molecules of silver ion to be reduced.
Included within the class of dye-forming couplers are colored
couplers that have a color correcting capability, as well as
compounds that release photographically useful fragments upon
coupling with the oxidation product of developing agents. Among
these compounds, those which release development retarders as a
function of development to improve the sharpness or granularity of
image are called "DIR couplers".
In place of DIR couplers, DIR compounds that form colorless
compounds as well as release development retarders upon coupling
reaction with the oxidation product of developing agents may be
used. Included within the class of useful DIR couplers and DIR
compounds are compounds that are commonly referred to as "timing
DIR couplers" and "timing DIR compounds". Development retarders
released may be diffusible or may not be highly diffusible and
these two types of retarders may be used either on their own or as
admixtures depending on a specific object. Competitive couplers, or
colorless couplers that enter into a coupling reaction with the
oxidation product of aromatic primary amino compounds as developing
agents but which will not form dyes, may be used in combination
with dye-forming couplers.
Preferred yellow dye forming couplers may be selected from the
class of known acylacetanillde containing couplers, among which
benzoylacetanilide- and pivaloylacetanilide-containing compounds
are particularly preferred. Useful magenta dye forming couplers
include known 5-pyrazolone containing couplers,
pyrazolobenzimidazole containing couplers, pyrazolotriazole
containing couplers, open-chain acylacet-onitrile containing
couplers, indazolone containing couplers, etc. Useful cyan dye
forming couplers include known phenolic and naphtholic couplers, as
typically exemplified by phenolic couplers substituted by, for
example, alkyl, acylamino or ureido group, naphtholic couplers
comprising a 5-aminonaphthol skeleton, and two-equivalent
naphtholic couplers having an oxygen atom introduced in a leaving
group.
The photographic material of the present invention which contains
the silver halide emulsion defined hereinabove can be produced
using known supports that have a high degree of flatness and that
are so dimensionally stable as to experience little dimensional
change during either manufacture or processing. Examples of such
supports include cellulose nitrate films, cellulose ester films,
polyvinyl acetal films, polystyrene films, polyethylene
terephthalate films, polycarbonate films, glass, paper, metals and
paper coated with polyolefins such as polyethylene and
polypropylene. In order to provide improved adhesion to
photographic emulsion layers, these supports may be subjected to
various surface treatments that render them hydrophilic, such as
saponification, corona discharge, subbing and setting.
The photographic material of the present invention can be processed
using known photographic processing methods and solutions such as
those described in Research Disclosure (RD) No. 17643, Item 176,
pp. 20-30, December 1978. The photographic processing methods used
may be black-and-white photography for producing silver image or
color photography for producing dye image. The processing
temperature typically ranges from 18.degree. to 50.degree. C. but
satisfactory processing can be accomplished even if the temperature
is lower than 18.degree. C. or higher than 50.degree. C.
Various color and black-and-white photographic materials can be
produced using the silver halide emulsion defined hereinabove.
The present invention is particularly suitable for producing
high-sensitivity color photographic materials. It is preferred to
employ the following techniques in producing multi-layered color
photographic materials: the technique of modifying the order of
layer arrangement for achieving high sensitivity and high image
quality at the same time; the technique of further improving
granularity by dividing an emulsion layer having sensitivity to
light of a certain color into three sub-layers; and the technique
of further enhancing the sensitivity of a high-sensitivity layer,
particularly a highly blue-sensitive layer, by providing an
underlying reflective layer composed of fine silver halide grains.
Among these techniques, those relating to the order of layer
arrangement are described in such prior patents as U.S. Pat. Nos.
4,184,876, 4,129,446, 4,186,016, BP No. 1,560,965, U.S. Pat. Nos.
4,186,011, 4,267,264, 4,173,479, 4,157,917, 4,165,236, BP No.
2,138,962, Unexamined Published Japanese Patent Application No.
177552/1984, BP No. 2,137,372, and Unexamined Published Japanese
Patent Application Nos. 180556/1984 and 204038/1984. The technique
concerning reflective layers is described in Unexamined Published
Japanese Patent Application No. 160135/1984.
The following examples are provided for the purpose of further
illustrating the present invention but are in no way to be taken as
limiting.
EXAMPLE 1
Using an apparatus of the type described in Unexamined Published
Japanese Patent Application No. 160128/1987, a monodispersed,
core/shell silver iodobromide emulsion (octahedral normal crystals;
grain size as calculated for cubes, 1.0 .mu.m; coefficient of
variation in grain size, 16%; average AgI content, 9.5 mol %; high
internal I content) was prepared.
The emulsion was divided into equal portions and to each portion,
140 mg of spectral sensitizers (D-1, D-2 and D-3),
3.2.times.10.sup.-4 moles of ammonium thiocyanate,
3.0.times.10.sup.-6 moles of sodium thiocyanate and
8.0.times.10.sup.-8 moles of a gold compound (see Table 1 below)
were added per mole of silver halide. The portions of the emulsion
were subjected to optimum sulfur-plus-gold sensitization at
55.degree. C. Thereafter. 850 mg of 4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene was added as a stabilizer. ##STR4##
Subsequently, a magenta coupler
{1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamido)benzamido]-
5-pyrazolone} and a colored magenta coupler
[1-(2,4,6-trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuci
nimidoanilino)-5-pyrazolone] were weighed in respective amounts of
80 g and 2.5 g per mole of silver halide and mixed with 120 g of
tricresyl phosphate and 240 mg of ethyl acetate. The resulting
mixture was heated and dispersed in a mixture of sodium
triisopropylnaphthalenesulfonate (5 g) and 7.5% aqueous gelatin
(550 ml). The thus formed coupler dispersion was added to the
previously prepared emulsion samples.
Further, an appropriate amount of 2-hydroxy-4,6-dichlorotriazine
sodium was added to each of the emulsion samples as a hardener and
the resulting emulsions were applied onto subbed triacetate
cellulose supports in a silver deposit of 2.0 g/m.sup.2 and dried,
whereby samples 1-7 were obtained.
Each of the thus obtained samples was divided into three parts: one
part was left to stand for one day under natural conditions; the
second part was aged under accelerated conditions by storage at
55.degree. C. and at 204% r.h. for 3 days; and the third part was
exposed to 100 mR of gamma-rays from 60 Co so as to estimate the
effect of natural radiations. The thus conditioned samples were
exposed through an optical wedge in the usual manner, color
developed in accordance with the scheme shown below, and had their
photographic performance evaluated. The results are shown in Table
1, in which "sensitivity" is expressed in terms of relative values,
with the sensitivity of Comparative Sample 1 (left to stand at room
temperature for one day under natural conditions) being taken as
100.
______________________________________ Processing scheme (at
38.degree. C.) Steps Time ______________________________________
Color development 3 min and 15 sec Bleaching 6 min and 30 sec
Washing 3 min and 15 sec Fixing 6 min and 30 sec Washing 3 min and
15 sec Stabilizing 1 min and 30 sec Drying
______________________________________
The color developing, bleaching, fixing and stabilizing solutions
used had the following compositions.
______________________________________ Color developing solution
4-Amino-3-methyl-N-ethyl-N-.beta.- 4.75 g hydroxyethylaniline
sulfate Anhydrous sodium sulfite 4.25 g Hydroxylamine hemisulfate
2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g
Nitrilotriacetate trisodium salt 2.5 g (monohydrate) Potassium
hydroxide 1.0 g Water to make 1,000 ml pH adjusted to 10.6 with
NAOH Bleaching solution Ethylenediaminetetraacetic acid iron 100.0
g ammonium salt Ethylenediaminetetraacetic acid 10.0 g diammonium
salt Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water to
make 1,000 ml pH adjusted to 6.0 with aqueous ammonia Fixing
solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6
g Sodium metasulfite 2.3 g Water to make 1,000 ml pH adjusted to
6.0 with acetic acid Stabilizing solution Formaldehyde (37% aq.
sol.) 1.5 ml Konidax (Konica Corp.) 7.5 ml Water to make 1,000 ml
______________________________________
TABLE 1
__________________________________________________________________________
1-day 3-day standing standing Exposure under natural at 55.degree.
C. and to .gamma.-rays Sample Gold conditions 20% r.h. (100 mR) No.
compound fog sensitivity fog sensitivity fog sensitivity Remarks
__________________________________________________________________________
1 Comparative 0.15 100 0.35 70 0.23 85 Comparison compound 1 2
Comparative 0.14 102 0.25 85 0.21 87 Comparison compound 2 3
Compound I-1 0.14 98 0.18 97 0.18 95 Invention 4 Compound I-3 0.14
105 0.20 100 0.17 100 Invention 5 Compound I-5 0.14 100 0.19 95
0.17 98 Invention 6 Compound I-6 0.14 110 0.20 100 0.18 105
Invention 7 Compound I-15 0.15 112 0.20 105 0.18 110 Invention
__________________________________________________________________________
Comparative compound 1: HAuCl.sub.4.4H.sub.2 O Comparative compound
2: Na.sub.3 [Au(S.sub.2 O.sub.3).sub.2
As is clear from Table 1, samples 3-7 using compounds within the
scope of the present invention were more stable to heat and
gamma-rays (natural radiation) than samples 1 and 2 using the
comparative compounds. Similar results were obtained when the
emulsions for samples 1-7 were used in green-sensitive emulsion
layers in multi-layered color photographic materials.
EXAMPLE 2
Emulsions comprising tabular monodispersed silver iodobromide
grains were prepared by a double-jet method as in Example 1. The
tabular grains had an average iodine content of 10.0 mol % (high
internal I content), a grain size of 1.2 .mu.m as calculated for
cubes, a coefficient of variation of 24% in grain size, and a
diameter to thickness ratio of 4.0.
Subsequently, the gold compounds used were evaluated as in Example
1. In Example 2, 1-ethyl-3-(2-thiazolyl)thiourea was used as a
sulfur sensitizer in place of sodium thiosulfate. The results of
evaluation are shown in Table 2, in which "sensitivity" is
expressed in terms of relative values, with the sensitivity of
sample 8 being taken as 100.
As is clear from Table 2, samples 10-13 using compounds within the
scope of the present invention were more stable to heat and
gamma-rays (natural radiation) than samples 8 and 9 using the
comparative compounds.
TABLE 2
__________________________________________________________________________
1-day 3-day standing standing Exposure under natural at 55.degree.
C. and to .gamma.-rays Sample Gold conditions 20% r.h. (100 mR) No.
compound fog sensitivity fog sensitivity fog sensitivity Remarks
__________________________________________________________________________
8 Comparative 0.14 100 0.30 75 0.20 85 Comparison compound 1 9
Comparative 0.14 100 0.23 87 0.19 90 Comparison compound 2 10
Compound I-1 0.13 100 0.17 99 0.17 98 Invention 11 Compound I-3
0.14 105 0.18 100 0.18 98 Invention 12 Compound I-5 0.13 100 0.19
98 0.17 99 Invention 13 Compound I-6 0.13 105 0.19 99 0.18 102
Invention
__________________________________________________________________________
*Comparative compounds 1 and 2 were the same as in Example 1.
EXAMPLE 3
A core/shell tetradecahedral grain emulsion with 2 mol % AgI (high
internal I content; grain size as calculated for cubes, 1.0 .mu.m;
coefficient of variation in grain size, 18%) was prepared as in
Example 1.
Subsequently, the emulsion was divided into equal portions and to
each portion, 4.4.times.10.sup.-6 moles of sodium thiosulfate,
1.2.times.10.sup.-3 moles of ammonium thiocyanate and
1.2.times.10.sup.-6 moles of a gold compound (see Table 3) were
added per mole of silver halide. The portions of the emulsion were
subjected to optimal sulfur-plus-gold sensitization at 55.degree.
C.
After chemical ripening, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene
(stabilizer), saponin (coating aid) and
2,4-dichloro-6-hydroxy-s-triazine (hardener) were added in
appropriate amounts to each emulsion. The resulting emulsions were
applied onto subbed polyester supports and dried to prepare samples
14-19.
Each of the thus prepared samples was divided into three parts: one
part was left to stand for one day under natural conditions; the
second part was aged under accelerated conditions by storage at
55.degree. C. and at 20% r.h. for 3 days; and the third part was
exposed to 100 mR of gamma-rays from 60 Co.
The thus conditioned samples were exposed through a conventional
sensitometric wedge for 1/50 sec and subsequently developed with a
developing solution (see below) at 35.degree. C. for 30 sec.
Following fixing, washing and drying, the photographic performance
of the processed samples was evaluated for sensitivity and fogging,
with the results being shown in Table 3.
Photographic sensitivity is expressed by the reciprocal of the
logarithm of the amount of exposure necessary to provide an optical
density of (fog+0.1) and in Table 3, "sensitivity" is expressed in
terms of relative values, with the sensitivity of sample 14 being
taken as 100.
______________________________________ Developing solution for
black-and-white photography ______________________________________
1-Phenyl-3-pyrazolidone 1.5 g Hydroquinone 30.0 g 5-Nitroindazole
0.25 g Potassium bromide 5.0 g Anhydrous potassium sulfite 55.0 g
Potassium hydroxide 30.0 g Boric acid 10.0 g Glutaraldehyde (25%)
5.0 g Water to make 1,000 ml
______________________________________
TABLE 3
__________________________________________________________________________
1-day 3-day standing standing Exposure under natural at 55.degree.
C. and to .gamma.-rays Sample Gold conditions 20% r.h. (100 mR) No.
compound fog sensitivity fog sensitivity fog sensitivity Remarks
__________________________________________________________________________
14 Comparative 0.02 100 0.05 98 0.04 97 Comparison compound 1 15
Compound I-1 0.01 102 0.02 106 0.02 104 Invention 16 Compound I-3
0.01 100 0.02 103 0.02 103 Invention 17 Compound I-5 0.01 107 0.02
108 0.02 105 Invention 18 Compound I-6 0.01 110 0.02 110 0.03 105
Invention 19 Compound I-15 0.02 115 0.03 120 0.03 110 Invention
__________________________________________________________________________
*Comparative compound 1 was the same as used in Example 1.
As Table 3 shows, samples 15-19 using compounds within the scope of
the present invention were more stable to heat and .gamma.-rays
than sample 14 using comparative compound 1.
* * * * *